JPS61158839A - Glass composition - Google Patents

Abstract

PURPOSE:A glass composition for ceramic bonding, having high bond strength between ceramic and ceramic or ceramic and metal, and small reduction in bond strength even at specific high temperature, having a specified composition. CONSTITUTION:A glass composition for ceramic bonding comprising (A) 100pts. wt. at least one powder of TiN, TiB2, AlN, AlB2, BN, B4C, SiC, and Si3N4, (B) 20-160pts. wt. SiO2 powder, (C) 1-600pts. wt. B2O3 powder, and (D) 1-1,600pts. wt. at least one of (R1)2O, (R2)O, (R3)O2 and (R4)2O2(R1 is Na, K, or Li; R2 is Mg, Ca, Ba, Zn, Pb, or Cd; R3 is Ti, Zr, or Mn; R4 is Al, or bi). This composition is laid between target materials, and heat-treated to give a bonded material having high bond strength the bonded material has characteristics of approximately no reduction in bond strength even if it is heated to 400-1,000 deg.C high temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a glass composition for bonding ceramics to ceramics or metals.

BACKGROUND OF THE INVENTION In recent years, the development of ceramic materials has progressed, and ceramics have come to be used in a wide range of fields such as electronic parts, tools, mechanical parts, building materials, and household goods. Along with these advances in ceramic materials, in order to use ceramics for even more applications, it is essential to advance advanced secondary processing technology such as bonding technology between ceramics and other ceramics and metals. Become.

Conventionally, the following methods are known as methods for joining ceramics and ceramics or metals. (1) A method using an organic adhesive, (2) a method using glass enamel as an adhesive, and (3) a method of fusing at high temperature.

However, in method (1), the operating temperature of the bonded product is limited to 200 to 800°C or less, and in method (2), the objects to be bonded are a combination of oxide ceramics and oxide ceramics or metals. In addition, the bonding strength is low, especially at temperatures above aoo°C, and the bonding strength decreases markedly.In method (3), the ceramics and metals deform when ω is observed, so the range of use is limited. There are drawbacks.

In addition, attempts have been made to apply ceramics to a wider range of fields by plating them to form a metal film and imparting conductivity to the ceramics, but the bonding strength between the ceramics and the metal film is low. Therefore, it has not been put into practical use.

Means for Solving the Problems In view of the problems of the prior art as described above, the inventor of the present invention has conducted intensive research and has developed a method in which a glass composition having a specific composition is interposed between the objects to be joined. By heat treatment,
A bonded body with high bonding strength was obtained, and the bonded body was
Even if heated to a high temperature of 0 to 1000°C, there is almost no decrease in bonding strength, and the ceramics to be bonded are
It has been found that a bonded body having high bonding strength can be obtained not only when using oxide-based ceramics but also when non-oxide-based ceramics are used. Furthermore, the present inventors have discovered that by disposing the glass composition on ceramics, heat-treating the composition, and then forming a plating film thereon, the plating film can be firmly bonded to the ceramics.

That is, the present invention provides Ill TiN, TIBI, AIN, AlB2, BN
%n, c, sic and s i , 1 ooB parts by weight of at least one powder of R4, (II 8i02% powder 20-16oo parts by weight, +m
l B 20. Powder 1-600 parts by weight, and 11v
l (R1)to, (Rz)0, (Rs)Ox and (
R4) zOs (where R1 is Na, K or Li,
, tt, is Mg, Ca, Ba, zn%Pb or C
d%R, is Ti%zr or Mn, R4 is A) or Bi) powder 1-1600
The present invention relates to a glass composition for bonding ceramics consisting of parts by weight.

In the present invention, TiN, TiB snow, AIN, AlBs
%BN.

It is essential to blend at least one powder of R40,8jO and s i 8N4 into the glass composition. By using this glass composition to bond ceramics and metals, it is possible to bond not only oxide ceramics (but also non-oxide ceramics), and the strength of the bond can be increased. Further, when the glass composition is coated on ceramics and heated, the non-oxide powder becomes scattered in the shape of islands in the glass composition, and a plating film is formed on this. The bonding strength is significantly improved when

In the present invention, TiN, TiBz, A/N%AI! B
2.BN.

+a+ sio, 20 to 1600 parts by weight of powder for at least 100 parts by weight of powder of at least one of 13ac, sic and si, R4 (
b) Bt Oa powder 1-600ftt! , and he (
CI (R1)! 0. (R1)0, (Ra)Ox
and (R4)zOa (death, R1 is Na%K 1 f
t41 Li, 84 g; tMg.

01%Ba, Zn%Fb, TahaCd%Rm, Ti%zr
Remember, Mn%R4 is AI! It is necessary to blend 1 to 1,600 parts by weight of at least one powder of (Bi or Bi). If the amount of each component is below the above range, the glass composition may not be vitrified or the bonding strength may be significantly reduced when the glass composition is heated, and if it exceeds the above range, the bonding strength may be significantly reduced. This is not desirable as there is a significant decrease.

As each component of the glass composition of the present invention, commercially available products can be used, and there are no particular limitations on the manufacturing method, particle size, purity, etc. However, in order to increase the bonding strength of the bonded product, high purity products may be used. It is preferable to use, the particle size is 0.1~l
It is preferable to use a material of about Q Q #m.

The method for producing the composition of the present invention is not particularly limited; for example, it is sufficient to simply mix the respective component materials using a mixer, a mill, etc.).

In addition, by mixing 2 or more randomly selected component substances, 7
After heating and melting at 00 to 1600° C. for 10 to 20 minutes, other components may be added to the powder obtained by crushing the powder to about 0.1 to 1 Q #m using a ball mill or the like.

In order to bond ceramics and ceramics or metals using the composition of the present invention, the composition of the present invention is first applied to the ceramics and/or metals.

The coating method is not particularly limited, and the following methods can be exemplified.

(Method of directly applying the 11 composition.

(Method of irradiating the 111 composition.

(till A method of dispersing the composition in a solvent such as alcohol or acetone and spray painting.

(1v) A method of dipping the composition into an organic vehicle and then immersing ceramics and/or metals in the dispersion. A solution of an organic polymer compound such as ethyl cellulose acrylic resin in an organic solvent such as inpropyl alcohol, pine oil, butylcalcitol acetate can be used. It is preferred that the coating density of the composition of the present invention be 0.005 to 277/Cm''.

Next, ceramics and/or metals to be joined are brought into contact with the composition of the present invention and then heated.

The heating temperature is 500-1500℃, and the heating time is 8-1500℃.
It will take about 60 minutes. The atmosphere during heating is not particularly limited, and may be, for example, an atmosphere of air, nitrogen gas, hydrogen gas, argon gas, or the like.

Ceramics and metals to which the composition of the present invention can be applied may have a heat resistance temperature of 500° C. or higher, and there are no other restrictions. Also, the shape is not limited; powder, rod, plate, etc.
It can be applied to all shapes of ceramics and metals, such as molded products. Specific examples of ceramics to which the composition of the present invention can be applied include tiles, portral cement, bricks,
So-called old ceramics such as straw, ceramics, and enamel containers, alumina, zirconia, beryllia, mullite, holsterite, coprite, magnesia, ferrite, zinc oxide, soot oxide, lead titanate, barium titanate, lead zirconate titanate, etc. Oxide ceramics, silicon nitride, silicon carbide, boron nitride, aluminum nitride, boron carbide, tungsten carbide, titanium nitride, thallium carbide, calcium carbide, titanium boride, lanthanum boride, cas 1 z 1Mn8 i
Examples include non-oxide ceramics such as calcium 2.7'/oxide and calcium sulfate. Examples of metals include ordinary metals and alloys such as e, cap, nickel, stainless steel, titanium alloy, copper alloy, carbon-silicon steel, chromium steel, nickel steel, manganese steel, tungsten-carbide. Sintered alloys made by powder metallurgy such as alloys, titanium-carnoite alloys, and molybdenum alloys (Mo-Ag, MO-Ou, etc.) can also be used.

The composition of the present invention can also be used to bond ceramics and plated metal films. When used for joining ceramics and plating film, first apply
After applying the composition of the present invention, it is heat-treated. The coating method and heating method may be the same as those for joining ceramics to ceramics or metal samples. Next, after the ceramics have been prepared, a plating film is formed on the glass composition according to a conventional method. Examples of the plating method include a method of applying electroless nickel or fine TPS copper plating after depositing a catalyst substance, and a method of dry plating such as vapor deposition or sputtering.After forming a plating film,
Further, a thick metal film may be formed by electroplating or the like, or a conductive material such as another metal may be joined by methods such as soldering or brazing.

Effects of the Invention By bonding ceramics using the glass composition of the present invention, the following excellent effects are achieved.

(1) The bonding strength between ceramics and ceramics or metals is high, and the decrease in bonding strength is extremely small even when directly heated at 400 to 1000°C.

(2) Applicable to both oxide ceramics and non-oxide ceramics.

(3) Ceramics and plating film can be firmly bonded.

(4) The heating source ranges from 500 to 1500°C.

The glass composition of the present invention has excellent properties as described above and can be applied to a wide range of fields. An example is shown below.

It is used as a building material by bonding the whole or part of the wood.

(bl) Metal parts are bonded to an enamel container and used as a household item.

(cl) Metals with high strength are bonded with ceramics that are resistant to rust, have low heat conductivity, and have excellent wear resistance, and are used as tools such as electric irons, files, and cutlery.

idl In mechanical materials such as rotary pump cylinders, the metal outer mold and inner ceramic material are joined together.

(el) In a ceramic engine, ceramic parts are joined to the engine body.

By bonding Yama ceramics to a copper plate, it can be used as an electrical material for large current printed circuit boards, etc.

(As for bonding ceramics and plating film, J
It is used for manufacturing ceramic substrates, parts for printers, and forming electrodes on ceramics.

Example Hereinafter, the present invention will be explained in more detail by showing examples.

Example 1 TiN 100 overlapping part with a particle size of 20 μm, a particle size of 51 m (
D 8i02600 parts by weight, B20a with a particle size of 5 am
A glass composition consisting of an aO layered part, a caoiooo layered part with a grain size of about 5 μm, 20 parts by weight of TiO2 with a grain size of 10 μm, and 1 part by weight of Al2O5 with a grain size of 10 μm was sxa
0.2i/Cm on 96% alumina sintered plate of xtcm
After coating the alumina sintered plate at a ratio of 1 cm, a zirconia sintered rod with a diameter of 1 cm was placed vertically on top of the alumina sintered plate and heated at 880°C for 25 minutes to bond the alumina sintered plate and the zirconia sintered rod. Next, the bonding strength was determined by pulling the zirconia plate perpendicularly to the alumina plate at each temperature of 25°C and 450°C and measuring the strength when the plate was released. The results are shown in Table 1.

Example 2 100 parts by weight of TiB with a particle size of 50 μm, particle size ';l
Q pm sio, tso heavy base, particle size 10 am
40 parts by weight of B2O3, 20 μm particle size Na202
0 parts by weight, l! lfr & approx. 20 am (7) Ba01
A glass composition consisting of a part by weight of Pb060 with a grain size of 15 μm and a Bi 20B 12 tm part with a grain size of 20 μm was thermally sprayed onto an 8 x 8 x 1 cm stainless steel/bonded metal plate at a ratio of 970 m2, and then sprayed onto this. A silicon nitride sintered body with a diameter I Crn was placed on duty and heated at 670°C for 10 minutes to join the stainless steel sintered Li plate and the silicon nitride sintered body. The bonding strength was determined by the same method as in Example 1, and the results are shown in Table 1.

Example 8 Particle size 1 #rn 0) Part by weight of 81027, part of Bg03201 with particle size of 0.5 pm, part of Li2° x 7.5 im with particle size of about 0.5 μm, MgO7 with particle size of 1 μm,
A powder consisting of a five-layer base, 12.5 parts by weight of PBO with a grain size of 1 μm, and a ZrO2101 base with a grain size of 3 μm was placed in a platinum crucible, heated at 1300°C for 80 minutes, and then melted. This melt was ground in a ball mill to form a powder of 5 to 30 μm, and then mixed with 100 parts by weight of A/N having a particle size of 10 μm to obtain a glass composition of the present invention. Next, 80 parts by weight of the glass composition was added to a mixed solvent consisting of 10 parts by weight of methanol and 10 parts by weight of isopropyl alcohol, and the composition was sprayed onto a 96% alumina sintered plate of 3×8XI Cm while stirring mechanically. Equipment is 0.5J//
Then, a copper rod with a diameter of t cm was placed vertically on top of this and heated at 600°C in nitrogen gas.
The alumina plate and the copper rod were joined by heating for 5 minutes.

Table 1 shows the results of determining the bonding strength using the same method as in Example 1.

Example 4 Ntoo car short part with particle size of 5 μm, s with particle size of 5gn
io, 100 parts by weight, particle size 8 jlrn (7)
7 parts by weight of B20g, 10 parts by weight of Kgo with a particle size of 5 μm, parts by weight of ZnOa with a particle size of 1 μm, 10 μm in particle size
3 parts by weight of Mn O2 and 8 μm in particle size Al! 20
A glass composition of the present invention consisting of 4 parts by weight of B, 80 parts by weight and an organic vehicle 2 (11 parts by weight) consisting of 70% by weight of ethyl cellulose and 80% by weight of pine oil are mixed well;
A glass composition of the present invention was brushed onto a silicon carbide sintered plate of 8×8×1 cm to give a ratio of Q, l Ii/Cm2. Next, a rod of silicon carbide sintered body with a diameter of 1 cm was vertically placed on top of this and heated at 920° C. for 40 minutes to join the silicon carbide sintered plate and the silicon carbide rod. The results of determining the bonding strength using the same method as in Example 1 are shown in the first example.
Shown in the table.

Example 5 10 parts by weight of SIC of 60 μm in particle size, 20 parts by weight in particle size
, 5i02186 parts by weight of gm, B of particle size 25#m
20fi61t: ht part, grain, ZrO2 with a diameter of about 5 μm
A glass composition consisting of 141 parts by weight and 20 parts by weight of AlzOs with a particle size of 10 μm was placed in a platinum crucible and heated to 1500
The mixture was melted by heating at ℃ for 45 minutes, and then cooled and ground in a ball mill to obtain a powder having a particle size of 10 to 10011 m.

This powder was applied to a silicon carbide 3c sintered body of a x 8 x 1 cm at a density of 0.08 p/cm! After applying at the rate of 1
Heated at 200°C for 5 minutes. After the silicon carbide sintered body was cooled to room temperature, electroless copper plating was performed using the method described below.

(1) Degreasing: Immerse in alcohol solution for 5 minutes and then.

Addition of Ti1l catalyst: sensitizer liquid at 25℃, 8
After being immersed for a minute, it was washed with water, and after being immersed in an activator solution at 25° C. for 2 minutes, it was washed with water. As the sensitizer liquid, a 100 mz7z aqueous solution of Sensitizer (trademark "TMP Sensitizer" manufactured by Okuno Pharmaceutical Co., Ltd.) was used, and as the activator liquid, Activator (trademark "T") was used.
M P Activator” (manufactured by Okuno Pharmaceutical Co., Ltd.) 100
Use ml/l aqueous solution.

1 [111 Electroless nickel plating: Electroless nickel plating solution (trademark "Top Nicolon EL-70", manufactured by Okuno Pharmaceutical Co., Ltd.) 4 o ml/l Aqueous solution was immersed at 90°C for 80 minutes.

After electroless nickel plating is formed, a diameter of 1 cm is applied on top of this.
m iron rods are stood vertically and brazed at 850℃,
By pulling an iron rod perpendicularly to the silicon carbide sintered body at each temperature of 5°C and 450°C, the strength of the plating film was measured when #J was removed from the silicon carbide sintered board. The joint strength was determined. The results are shown in Table 1.

Example 6 8j02189 heavy lid with particle size of 80#m, particle size of 10
am O) B20g 28 parts by weight, particle size 10 am
0 dO 14 parts by weight, particle size 20 am Tio,
28 parts by weight of B120a with a heavy weight and a particle size of approximately 5 μm
A powder consisting of was heated and melted in a platinum crucible at 1450°C for 30 minutes. Then, after this melt has cooled.

Pulverize with a ball mill to obtain a powder of 1 to 10 μm, and add Si3N466 imjt part and AJ with a particle size of 1 to 10 #m.
17 parts by weight of Bi and 17 parts by weight of B2O were added and mixed to obtain a glass composition. Next, 191 parts of an organic vehicle consisting of 851% ethyl cellulose and 151% Vine oil were added to 100 parts of the glass composition and mixed, and the resulting composition was passed through 3 rolls 8 times.
Using a mesh screen, the composition of the present invention was applied to one plane of a 5 x 6 x 1 cm silicon nitride sintered body at a rate of 0.02 y/cm.
cm2, and preheated at 150°C for 5 minutes, then heated at 900°C for 5 minutes. Metal tin was applied in a circular shape with a diameter of 1 cm at 0.00877/C on four places on the surface coated with the glass composition in this way.
m @ After vapor deposition, 6 is added to electrostatic nickel plating solution.
A nickel plating film was formed on the gold 4114 tin by immersion at 0°C for 60 minutes. The bonding strength between the silicon nitride compact, the nickel plating fy, and the film was measured using the same method as in Example 5. Eight fruits are shown on the back and front.

Example 7 In the same manner as in Example 6, an organic vehicle and a glass composition were mixed to obtain a composition of 5 x 5 x O, and a 200 mesh screen was applied to a 1 cm alumina plate to obtain a composition of the present invention of 0.008. g/Cm2 After screen printing, preheat at 150°C for 10 minutes and then heat to 870°C.
After heating for 20 minutes and cooling the alumina plate to room temperature, it was coated with an electroless plating medium (trademark "C0P-4280").
Back! ! 25°C for 5 minutes,
It was heated at 200°C for 10 minutes, and then, after reaching room temperature, it was immersed in a Kabu electrolytic copper plating solution (trademark "OPO Copper", manufactured by Okushi Pharmaceutical Industry Co., Ltd.) at 55°C for 30 minutes to form a copper plating film. . Next, conduct electric cap plating to achieve a copper plating thickness of 40 mm.
μm, screen-print masking ink (trademark "Top Resist G" manufactured by Okuno Pharmaceutical Co., Ltd.) in 5 places on the copper plating surface in a double layer square shape, and then UV
The masking ink was cured by irradiation for 10 seconds. This sample was immersed in a ferric chloride aqueous solution at 50°C,
The copper-plated parts other than the masking parts were dissolved and then immersed in a methylene chloride solution to peel off the masking ink. The bonding strength between the remaining copper plating film and the alumina plate was measured in the same manner as in Example 5, and the results are shown in Table 1.

Comparative Example 1 Table 1 shows the results of measuring the bonding strength between the zirconia rod and the alumina plate in the same manner as in Example 1 except that a composition obtained by removing TiN from the glass composition used in Example 1 was used. .

Juice l cavity a9 The results of determining the bonding strength between the stainless steel sintered alloy plate and the silicon nitride rod in the same manner as in Example 2 except that a composition was used in which TiB2 was removed from the glass composition used in Example 2. Shown in Table 1.

Comparative Example 3 AI! from the glass composition of Example 8! The bonding strength between the alumina plate and the copper rod was determined in the same manner as in Example 8 except that a composition excluding N was used, and the results are shown in Table 1.

Comparative Example 4 The bonding strength between the silicon carbide sintered body and the oxidized silicon rod was determined in the same manner as in Example 4 except that a composition in which BN was removed from the glass composition of Example 4 was used. It is shown in Table 1.

Comparative Example 5 The bonding strength between the silicon carbide sintered body and the button plating film was measured in the same manner as in Example 5 except for using the glass composition of Example 5 except that SiC was removed. Shown in the table.

Comparative Example 6 The glass composition of Example 5 was not used, and the rest was Example 5.
The results of measuring the bonding strength between the silicon carbide sintered body and the copper plating film in the same manner as above are shown in the Wt table.

Comparative Example 7 The bonding strength between the silicon nitride sintered body and the nickel plating film was determined in the same manner as in Example 6 except that a composition in which 811N4, A/B, and B4C were removed from the glass composition of Example 6 was used. The measured results are shown in Table 1.

Ratio Example 8 A silicon nitride sintered body and a nickel plating film were formed in the same manner as in Example 6, except that the silicon Vide sintered body was not screen-printed with a composition consisting of a glass composition and an organic vehicle. Table 1 shows the results of measuring the bonding strength.

Comparative Example 9 The bonding strength between the alumina plate and the copper plating film was measured in the same manner as in Example 7 except that 81 g of N4, A7B2 and B4C were removed from the glass composition of Example 6. Shown in the table.

Comparative Example 10 The bonding strength between the alumina plate and the copper plating film was measured in the same manner as in Example 7, except that the alumina plate was not patted with a composition consisting of a glass composition and an organic vehicle. It is shown in Table 1.

From Table 1 @ Table 1, it is clear that when the composition of the present invention is used, a bonded body with high bonding strength can be obtained, and there is little decrease in bonding strength even at the crystal temperature. In the example, it is clear that even if high bonding strength is obtained at 25°C, the bonding strength significantly decreases at 450°C.

(that's all) 2゛-1

Claims (1)

[Claims] (1) (i) TiN, TiB_2, AlN, AlB_2
, 100 parts by weight of at least one powder of BN, B_4C, SiC and Si_3N_4, (ii) 20 to 1600 parts by weight of SiO_2 powder, (ii
i) 1 to 600 parts by weight of B_2O_3 powder, and (iv)
(R_1)_2O, (R_2)O, (R_3)O_2 and (R_4)_2O_2 (R_1 is Na, K or Li, R_2 is Mg, Ca, Ba, Zn, Pb or Cd, R_3 is Ti, Zr or Mn, R_4 is Al
or Bi) powder 1-160
A glass composition for bonding ceramics consisting of 0 parts by weight.